Piperidine derivatives

ABSTRACT

A novel piperidine derivative having a stabilizing effect on a synthetic polymeric material and a composition comprising said piperidine derivative and a synthetic polymeric material.

This is a Division of application Ser. No. 405,570, filed Oct. 11, 1973U.S. Pat. No. 3,899,464.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a novel piperdine derivative and use thereofas stabilizer for polymeric materials.

More particularly, the piperidine derivatives of this invention has thefollowing formula: ##STR1## wherein R₁ represents hydrogen atom, analkyl group, a substituted alkyl group, an alkenyl group, an alknylgroup, a substituted or unsubstituted aralkyl group, an aliphatic acylgroup, an alkoxycarbonyl group or an aralkoxycarbonyl group, n is aninteger of 1 to 4; when n is 1, R₂ represents hydrogen atom, analiphatic, aromatic or heterocyclic monoacyl group, an alkyl group, analkenyl group, an alkynyl group, an aralkyl group, an aryl group, analkoxyalkyl group, an epoxyalkyl group, an alkoxysulfonylalkyl group, aN-substituted carbamoyl group, a N-substituted thiocarbamoyl group, amonovalent group from an oxoacid or group ##STR2## in which R₃represents hydrogen atom, a lower alkyl group or phenyl group and R₄represents an alkyl group; when n is 2, R₂ represents carbonyl group, analiphatic or aromatic diacyl group, an alkylene group, an alkenylenegroup, an alkynylene group, an aralkylene group, a N-substituteddicarbamoyl group or a divalent group from an oxoacid; when n is 3, R₂represents an aromatic triacyl group or a trivalent group from anoxoacid; and when n is 4, R₂ represents an aromatic tetracyl group, andA represents a group ##STR3## in which R₅ represents hydrogen atom or alower alkyl group or, when n is 1, R₅ may represent together with R₂ agroup ##STR4## in which R₆ represents the same group as defined in R₁and may be the same or different from R₁, or a group ##STR5## in which mis 1 or 2 and R₇ represents hydrogen atom or, when n and m are 1, R₇represents methylene group together with R₂.

The inventors of this invention have found that the piperidinederivatives of the above-mentioned formula (I) have a stabilizingeffect, especially an effectively preventive property from photo- andthermal-deterioration of synthetic polymeric materials such aspolyolefin, polyvinyl chloride, polyvinylidene chloride, polyacetal,polyester, polyamide, polyurethane, epoxy resin and the like.

The term "polymeric material" as used herein is intended to embrace

polyolefins including homopolymers of olefins such as low-density andhigh-density polyethylene, polypropylene, polystyrene, polybutadiene,polyisoprene and the like, and copolymers of olefins with otherethylenically unsaturated monomers such as ethylene-propylene copolymer,ethylene-butene copolymer, ethylenevinyl acetate copolymer,styrene-butadiene copolymer, acrylonitrile-styrene-butadiene copolymerand the like;

polyvinyl chlorides and polyvinylidene chlorides including homopolymerof each of vinyl chloride and vinylidene chloride, vinylchloride-vinylidene chloride copolymer and copolymers of each of vinylchloride and vinylidene chloride with vinyl acetate or otherethylenically unsaturated monomers;

polyacetals such as polyoxmethylene and polyoxyethylene;

polyesters such as polyethylene terephthalate;

polyamides such as 6-nylon, 6,6-nylon and 6,10-nylon; and

polyurethanes; and

epoxy resins.

Synthetic polymers have been widely utilized, owing to their excellentproperties, in various forms or shapes, for example, filament, fibre,yarn, film, sheet, other molded article, latex and foam.

The present piperidine derivatives of the above-mentioned formula (I),when more separately classified, include those compounds of thefollowing formulae; ##STR6## wherein R₁, R₂ and n are as defined above,and R'₅ represents hydrogen atom or a lower alkyl group; ##STR7##wherein R₁ and R₆ are as defined above, ##STR8## wherein R₁, R₂, n and mare as defined above, and ##STR9## wherein R₁ is as defined above.

In the above general formulae (II) to (V), each of R₁ andR₆ which isreferred to in (III) is an alkyl group having carbon atoms of 1-8, forexample, methyl, ethyl, propyl, butyl or octyl, preferably an alkylgroup having carbon atoms of 1-4, most preferably methyl; a substitutedalkyl group having carbon atoms of 1-3 in its alkyl, for example,2-hydroxyalkyl, e.g., 2-hydroxyethyl, alkoxyalkyl having carbon atoms of1-4 in its alkoxy, e.g., 2-ethoxyethyl or ethoxymethyl, saturatedaliphatic acyl having carbon atoms of 2-18, preferably 2-4, in its acyl,unsaturated aliphatic acyl having carbon atoms of 3-4 or acyloxyalkylhaving benzoyl, e.g., 2-acetoxyethyl, 2-stearoyloxyethyl,2-benzoyloxyethyl or 2-acryloyloxyethyl, and preferably 2-acetoxyethyl,2-acryloyloxyethyl or 2-benzoyloxyethyl; cyanoalkyl, e.g., 2-cyanoethylor cyanomethyl, halogenoalkyl, e.g., 2-chloroethyl, epoxyalkyl, e.g.,2,3-epoxypropyl, or alkoxycabonylalkyl having carbon atoms of 1-4 in itsalkoxy, e.g., methoxycarbonylmethyl, ethoxycarbonylmethyl,butoxycarbonylmethyl or 2-methoxycarbonylethyl; an alkenyl group havingcarbon atoms of 3-4, preferably allyl; an alkynyl group having carbonatoms of 3-4, preferably 2-propynyl; a substituted or unsubstitutedaralkyl group, for example, benzyl or halogeno- or methylsubstitutedbenzyl, preferably benzyl; a saturated or unsaturated aliphatic acylgroup having carbon atoms of 2-8, for example acetyl, propionyl,butyryl, acryloyl, methacryloyl or crotonoyl, preferably a saturatedaliphatic acyl having carbon atoms of 2-4 or an usaturated aliphaticacyl having carbon atoms of 3-4, most preferably acetyl; analkoxycarbonyl group having carbon atoms of 2-5, for example,ethoxycarbonyl or butoxycarbonyl; or an aralkoxycarbonyl group, forexample benzyloxycarbonyl. Particularly preferable R₁ is hydrogen atom,an alkyl group having carbon atoms of 1-4, allyl group, benzyl group, analkoxycarbonylmethyl group having carbon atoms of 1-4 in its alkoxy,2,3-epoxypropyl group, 2-saturated aliphatic acyloxyethyl group havingcarbon atoms of 2-18 in its acyl or an aliphatic acyl group havingcarbon atoms of 2-4. Hydrogen atom and methyl group are most preferable.

In the above formulae (II) and (IV), R₂ is, when n is 1 an aliphaticmonoacyl group such as a saturated aliphatic acyl group having carbonatoms of 1-18, preferably 2-18 in which sulfur atom may be put in theacyl chain or an unsaturated aliphatic acyl group having carbon atoms of3-6, of which the saturated or unsaturated aliphatic acyl may havephenyl substituted with alkyl having carbon atoms of 1-4 and/or hydroxyor unsaturated phenyl, for example, formyl, acetyl, propionyl,isobutyryl, octanoyl, lauroyl, stearoyl, acryloyl, methacryloyl,phenylacetyl, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl, sorboyl,cinnamoyl or 3-octylthiopropionyl and preferably saturated aliphaticacyl having carbon atoms of 2-18, most preferably 8-18, or an aromaticmonoacyl group, for example, benzoyl which may be substituted with alkylor alkoxy having carbon atoms of 1-4, halogen or hydroxy, e.g., benzoyl,o-, m- or p-toluoyl, p-t-butylbenzoyl, o-, m-or p-chlorobenzoyl,salicyloyl or o-, m- or p-anisoyl, or α-or β-naphthoyl, preferablybenzoyl which may be substituted with alkyl having atoms of 1- 4 orhydroxy, or a heterocyclic monoacyl group, for example, 2-furoyl,isonicotincyl, nicotinoyl or morpholincarbonyl; an alkyl group havingcarbon atoms of 1-18, for example, methyl, ethyl, propyl, butyl, hexyl,heptyl, octyl, dodecyl or stearoyl; an alkenyl group having carbon atomsof 3-4, preferably allyl; an alkynyl group having carbon atoms of 3-4,preferably 2-propynyl; an aralkyl group having carbon atoms of 7-8,preferably benzyl; an aryl group having carbon atoms of 6-11, forexample, phenyl o-, m- or p-tolyl or α- or β-naphthyl; an alkoxyalkylgroup having carbon atoms of 1-4, preferably 1-2, in its alkoxy and itsalkyl respectively, for example, methoxymethyl or ethoxymethyl; anepoxyalkyl group, preferably 2,3-epoxy propyl; an alkoxysulfonylalkylgroup having carbon atoms of 1-4 in its alkoxy and its alkylrespectively, for example, 3-methoxysulfonylpropyl; a N-substitutedcarbamoyl group or a N-substituted thiocarbamoyl group having asubstituent, for example, alkyl having carbon atoms of 1-4, e.g.,methyl, ethyl or butyl, aryl, e.g., phenyl or cycloalkyl, e.g.,cyclohexyl, preferably a carbamoyl group substituted with ethyl, phenylor cyclohexyl, a monovalent group from an oxoacid, such as, a groupderived from an oxoacid, e.g., substituted or unsubstituted sulfinicacid, sulfonic acid, phosphoric acid, phosphorous acid or phosphonicacid by removing one hydroxyl group and examples of the oxoacid arebenzenesulfinic acid, benzenesulfonic acid, p-toluenesulfonic acid,methanesulfonic acid, diphenylphosphoric acid, dialkylphosphoric acid ofC₁ -C₈ or diphenylphosphorous acid, dialkylphosphorous acid of C₁ -C₈,or a group ##STR10## wherein R₃ represents a lower alkyl group havingcarbon atoms of 1- 4, preferably methyl and R₄ represents an alkyl grouphaving carbon atoms of 1-8, for example, 2-ethoxycarbonylvinyl,1-methyl-2-methoxycarbonylvinyl, 1-methyl-2-octoxycarbonylvinyl or1-phenyl-2-ethoxycarbonylvinyl.

When n is 2, R₂ is a diacyl group such as a saturated aliphatic diacylhaving carbon atoms of 2-18, in which sulfur atom may be put in the acylchain or an unsaturated aliphatic acyl group having carbon atoms of 4-6,preferably a saturated aliphatic diacyl having carbon atoms of 4-12,e.g., oxalyl, malonyl, succinyl, adipoyl, suberoyl, sebacoyl,thiodipropionyl or fumaryl, an aromatic diacyl having 8 carbon atoms,e.g., terephthaloyl or isophthaloyl preferably terephthaloyl; analkylene group having carbon atom of 2-6, for example, ethylene,propylene, butylene or hexamethylene; an alkenylene group having carbonatoms of 4-6, for example, 2-butenylene; an aralkylene group havingcarbon atoms of 8-10, for example, p-xylylene; a N-substituteddicarbomoyl group having a substituent, for example, alkylene havingcarbon atoms of 2-6, e.g., ethylene, propylene, butylene orhexamethylene, or arylene having carbon atoms of 6-7, e.g., p-phenyleneor 2,4-tolylene, or p,p'-methanediphenylene, a divalent group from anoxoacid, e.g., sulfurous acid, sulfuric acid, substituted orunsubstituted sulfinic acid, sulfonic acid, phosphoric acid orphosphorous acid by removing two hydroxyl groups and examples of theoxoacid are sulfurous acid, sulfuric acid, phenylphosphorous acid.

When n is 3, R₂ is an aromatic triacyl having 9 carbon atoms, forexample, trimellitoyl or trimesoyl; or a trivalent group from anoxoacid, e.g., phosphoric acid, phosphorous acid or boric acid byremoving three hydroxyl groups, for example, ##STR11##

When n is 4, R₂ is an aromatic tetracyl group having 10 carbon atoms,for example ##STR12##

Particularly preferable R₂ is a saturated aliphatic acyl group havingcarbon atoms of 2-18, benzoyl group which may be substituted with alkylof C₁ -C₄ or hydroxy, an alkyl group having carbon atoms of 1-18, anallyl group, 2,3-epoxypropyl group, a saturated aliphatic diacyl grouphaving carbon atoms of 4-12, or terephthaloyl group. The lower alkylgroup of R'₅ in the formula (II) has preferably carbon atoms of 1-3 andis exemplified by methyl, ethyl or propyl, preferably methyl or ethyl.In the formula (II), n is preferred to be 1 or 2. In the formula (IV), nand m are preferred to be 1-2 and 1 respectively. ##STR13##

Representatives of the piperidine derivatives (1) of this invention areillustrated hereunder. However, these illustrated compounds are notintended to limit this invention.

The compounds of the formula (II).

    __________________________________________________________________________    II-1)                                                                              9-Aza-3-hydroxymethyl-8,8,9,10,10-pentamethyl-1,5-                            dioxa-spiro[5.5] undecane                                                II-2)                                                                              9-Aza-3-hydroxymethyl-3,8,8,10,10-pentamethyl-1,5-                            dioxa-spiro[5.5] undecane                                                II-3)                                                                              3-Acetoxymethyl-9-aza-3,8,8,10,10-pentamethyl-1,5-                            dioxa-spiro[5.5] undecane                                                II-4)                                                                              9-Aza-3-hydroxymethyl-3,8,8,9,10,10-hexamethyl-1,5-                           dioxa-spiro[5.5] undecane                                                II-5)                                                                              3-Acetoxymethyl-9-aza-3,8,8,9,10,10-hexamethyl-1,5-                           dioxa-spiro[5.5] undecane                                                II-6)                                                                              9-Aza-3-hydroxymethyl-3,8,8,10,10-pentamethyl-9-octyl-                        1,5-dioxa-spiro[5.5] undecane                                            II-7)                                                                              3-Acryloyloxymethyl-9-aza-3,8,8,10,10-pentamethyl-1,5-                        dioxa-spiro[5.5] undecane                                                II-8)                                                                              9-Aza-3-benzoyloxymethyl-3,8,8,10,10-pentamethyl-1,5-                         dioxa-spiro[5.5] undecane                                                II-9)                                                                              9-Aza-3-benzoyloxymethyl-3,8,8,9,10,10-hexamethyl-                            1,5-dioxa-spiro[5.5] undecane                                            II-10)                                                                             9-Aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-3-stearoyl-                          oxymethyl-spiro[5.5] undecane                                            II-11)                                                                             3-Acetoxymethyl-9-allyl-9-aza-3,8,8,10,10-pentamethyl-                        1,5-dioxa-spiro [5.5] undecane                                           II-12)                                                                             3-Acetoxymethyl-9-aza-3,8,8,10,10-pentamethyl-1,5-                            dioxa-9-(2-propynyl)-spiro [5.5] undecane                                II-13)                                                                             3-Acetoxymethyl-9-aza-9-cyanomethyl-3,8,8,10,10-                              pentamethyl-1,5-dioxa-spiro [5.5] undecane                               II-14)                                                                             9-Aza-3-(2,3-epoxypropyloxymethyl)-3,8,8,9,10,10-                             hexamethyl-1,5-dioxa-spiro [5.5] undecane                                II-15)                                                                             3-Acetoxymethyl 9-aza-9-(2,3-epoxypropyl)-3,8,8,10,10-                        pentamethyl-1,5-dioxa-spiro [5.5] undecane                               II-16)                                                                             3-Acetoxyme - pentamethyl-1,5-dioxa-spiro [5.5] undecane                 II-17)                                                                             9-(2-Acetoxyethyl)-3-acetoxymethyl-9-aza-3,8,8,10,10-                         pentamethyl-1,5-dioxa-spiro [5.5] undecane                               II-18)                                                                             3-Acetoxymethyl-9-aza-9-ethoxymethyl-3,8,8,10,10-                             pentamethyl-1,5-dioxa-spiro [5.5] undecane                               II-19)                                                                             9-Acryloyl-3-acryloyloxymethyl-9-aza-3,8,8,10,10-                             pentamethyl-1,5-dioxa-spiro [5.5] undecane                               II-20)                                                                             9-Aza-9-(p-chlorobenzyl)-3-hydroxymethyl-3,8,8,10,10-                         pentamethyl-1,5-dioxa-spiro[5.5]undecane                                 II-21)                                                                             9-Aza-3-ethyl-3-hydroxymethyl-8,8,10,10-tetramethyl-                          1,5-dioxa-spiro[5.5]undecane                                             II-22)                                                                             9-Aza-3-ethyl-3-hydroxymethyl-8,8,10,10-tetramethyl-                          9-(p-methylbenzyl)-1,5-dioxa-spiro[5.5]undecane                          II-23)                                                                             3-Acetoxymethyl-9-aza-3-ethyl-9-ethoxycarbonyl-                               methyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]-                            undecane                                                                 II-24)                                                                             9-Aza-3-ethyl-8,8,9,10,10-pentamethyl-3-(β-octyl-                        thiopropionyloxymethyl)-1,5-dioxa-spiro-[5.5]-                                undecane                                                                 II-25)                                                                             3-Acetoxymethyl-9-aza-3-ethyl-8,8,10,10-tetramethyl-                          1,5-dioxa-spiro[5.5]undecane                                             II-26)                                                                             3-Acetoxymethyl-9-aza-3-ethyl-8,8,9,10,10-pentamethyl-                        1,5-dioxa-spiro[5.5]undecane                                             II-27)                                                                             3-Acryloyloxymethyl-9-aza-3-ethyl-8,8,9,10,10-                                pentamethyl-1,5-dioxa-spiro[5.5]undecane                                 II-28)                                                                             9-Aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-3-                            stearoyloxymethyl-spiro[5.5]undecane                                     II-29)                                                                             3-Acetoxymethyl-9-aza-9-butoxycarbonyl-3,8,8,10,10-                           pentamethyl-1,5-dioxa-spiro[5.5]undecane                                 II-30)                                                                             3-Acetoxymethyl-9-aza-9-benzyloxycarbonyl-3,8,8,10,10-                        pentamethyl-1,5-dioxa-spiro[5.5]undecane                                 II-31)                                                                             9-Aza-3-(p-t-butylbenzoyloxymethyl)-3-ethyl-8,8,9,10,-                        10-pentamethyl-1,5-dioxa-spiro[5.5]undecane                              II-32)                                                                             9-Aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-3-                                   salicyloyloxymethyl-spiro[5.5]undecane                                   II-33)                                                                             9-Aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-3-                            salicyloyloxymetyl-spiro[5.5]undecane                                    II-34)                                                                             9-Aza-3-ethyl-8,8,9,10,10-pentamethyl-3-β-                               naphthoyloxymethyl-1,5-dioxa-spiro[5.5]undecane                          II-35)                                                                             9-Aza-3-(2-furoyloxymethyl)-3,8,8,9,10,10-                                    hexamethyl-1,5-dioxa-spiro[5.5]undecane                                  II-36)                                                                             9-Aza-3,8,8,9,10,10-hexamethyl-3-nicotinoyloxymethyl-                         1,5-dioxa-spiro[5.5]undecane                                             II-37)                                                                             9-Aza-3-benzenesulfinyloxymethyl-3,8,8,9,10,10-                               hexamethyl-1,5-dioxa-spiro[5.5]undecane                                  II-38)                                                                             9-Aza-3-mesyloxymethyl-3,8,8,9,10,10,-hexamethyl-                             1,5-dioxa-spiro[5.5]undecane                                             II-39)                                                                             9-Aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-3-                                   tosyloxymethyl-spiro[5.5]undecane                                        II-40)                                                                             9-Aza-3-hydroxymethyl-3,8,8,10,10-pentamethyl-9-                              iodomethyl-1,5-dioxa-spiro[5.5]undecane                                  II-41)                                                                             9-Aza-3-[β-(3,5-di-t-butyl-4-hydroxyphenyl)-                             propionyloxymethyl]-3,8,8,9,10,10-hexamethyl-1,5-                             dioxa-spiro[5.5]undecane                                                 II-42)                                                                             9-Aza-3-(3-methoxysulfonylpropyloxymethyl)-3,8,8,9,10,-                       10-hexamethyl-1,5-dioxa-spiro[5.5]undecane                               II-43)                                                                             9-Aza-3-ethyl-3-ethylcarbamoyloxymethyl-8,8,9,10,10-                          pentamethyl-1,5-dioxa-spiro[5.5]undecane                                 II-44)                                                                             9-Aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-3-                            phenylcarbamoyloxymethyl-spiro[5.5]undecane                              II-45)                                                                             9-Aza-3-cyclohexylthiocarbamoyloxymethyl-3-ethyl-                             8,8,9,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane                     II-46)                                                                             9-Aza-3,8,8,9,10,10-hexamethyl-3-octyloxymethyl-1,5-                          dioxa-spiro[5.5]undecane                                                 II-47)                                                                             9-Aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-3-stearyl-                           oxymethyl-spiro[5.5]undecane                                             II-48)                                                                             3-Allyloxymethyl-9-aza-3,8,8,9,10,10-hexamethyl-1,5-                          dioxa-spiro[5.5]undecane                                                 II-49)                                                                             9-Aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-3-(2-                                propynyloxymethyl)-spiro[5.5]undecane                                    II-50)                                                                             9-Aza-3-benzyloxymetyl-3,8,8,9,10,10-hexamethyl-1,5-                          dioxa-spiro[5.5]undecane                                                 II-51)                                                                             9-Aza-3-ethoxymethoxymethyl-3,8,8,10,10-pentamethyl-                          1,5-dioxa-spiro[5.5]undecane                                             II-52)                                                                             9-Aza-3-(β-ethoxycarbonylvinyloxymethyl)-3-ethyl-                        8,9,9,10,10-pentametyl-1,5-dioxa-spiro[5.5]undecane                      II-53)                                                                             9-Aza-3-(α-methyl-β-methoxycarbonylvinyloxymethyl)-                3,8,8,9,10,10-hexamethyl-1,5-dioxa-spiro[5.5]undecane                    II-54)                                                                             9-Aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-3-phenoxy-                           methyl-spiro[5.5]undecane                                                II-55)                                                                             Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                          spiro[5.5]-3-undecylmethyl)carbonate                                     II-56)                                                                             Bis(9-aza-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro-                            [5.5]-3-undecylmethyl)adipate                                            II-57)                                                                             Bis(9-aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-spiro-                           [5.5]-3-undecylmethyl)adipate                                            II-58)                                                                             Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                          spiro[5.5]-3-undecylmethyl)sebacate                                      II-59)                                                                             Bis(9-aza-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro-                            [5.5]-3-undecylmethyl)terephthalate                                      II-60)                                                                             Bis(9-aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-spiro-                           [5.5]-3-undecylmethyl)terephthalate                                      II-61)                                                                             Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                          spiro[5.5]-3-undecylmethyl)thiodipropionate                              II-62)                                                                             Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                          spiro[5.5]-3-undecylmethyl)sulfite                                       II-63)                                                                             1,2-Bis(9-aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-                             spiro[5.5]-3-undecylmethoxy)ethane                                       II-64)                                                                             1,4-Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-                            dioxa-spiro[5.5]-3-undecylmethoxy)-2-butene                              II-65)                                                                             α,α'-Bis(9-aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-                spiro[5.5]-3-undecylmethoxy)-p-xylene                                    II-66)                                                                             Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                          spiro[5.5]-3-undecylmethyl)hexamethylene-1,6-                                 dicarbamate                                                              II-67)                                                                             Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                          spiro[5.5]-3-undecylmethyl)tolylene-2,4-dicarbamate                      II-68)                                                                             Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                          spiro-[5.5]-3-undecylmethyl)diphenylmethane-p,p'-                             dicarbamate                                                              II-69)                                                                             Tris(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                         spiro[5.5]-3-undecylmethyl)trimesate                                     II-70)                                                                             Tris(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                         spiro[5.5]-3-undecylmethyl)phosphite                                     II-71)                                                                             Tetrakis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-                           dioxa-spiro[5.5]-3-undecylmethyl)pyromellitate                           II-72)                                                                             9-Aza-9-benzyl-3-ethyl-3-hydroxymethyl-8,8,10,10-                             tetramethyl-1,5-dioxa-spiro[5.5]undecane                                 II-73)                                                                             3-Acetoxymethyl-9-aza-9-benzyl-3-ethyl-8,8,10,10-                             tetramethyl-1,5-dioxa-spiro[5.5]undecane                                 II-74)                                                                             3-Acetoxymethyl-9-aza-3-ethyl-9-methoxycarbonyl-                              methyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane                II-75)                                                                             9-Aza-3-ethyl-3-stearoyloxymethyl-8,8,10,10-tetramethyl-                      1,5-dioxa-spiro[5.5]undecane                                             II-76)                                                                             9-Aza-3-benzoyloxymethyl-3-ethyl-8,8,10,10-tetramethyl-                       1,5-dioxa-spiro[5.5]undecane                                             II-77)                                                                             9-Aza-3-benzoyloxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-                     1,5-dioxa-spiro[5.5]undecane                                             II-78)                                                                             9-Aza-3-ethyl-3-salicyloxymethyl-8,8,10,10-tetramethyl-                       1,5-dioxa-spiro[5.5]undecane                                             II-79)                                                                             Bis[9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro-                      [5.5]-3-undecylmethyl]adipate                                            II-80)                                                                             Bis[9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-spiro-                    [5.5]-3-undecylmethyl]adipate                                            II-81)                                                                             Bis[9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro-                      [5.5]-3-undecylmethyl]terephthalate                                      II-82)                                                                             Bis[9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-                          spiro[5.5]-3-undecylmethyl]terephthalate                                 __________________________________________________________________________

The compounds of the formula (III).

    __________________________________________________________________________    III-1)                                                                             2,2,6,6-Tetramethylpiperidine-4-spiro-2'-(1','-                               dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-                                4"'-(2"',2"',6"',6"'-tetramethylpiperidine)                              III-2)                                                                             1,2,2,6,6-Pentamethylpiperidine-4-spiro-2'-                                   (1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-                               spiro-4"'-(1"',2"',2"',6"',6"'-pentamethylpiperidine)                    III-3)                                                                             2,2,6,6-Tetramethyl-1-octylpiperidine-4-spiro-                                2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-                               2"-spiro-4"'-(2"',2"',6"',6"'-tetramethylpiperidine)                     III-4)                                                                             2,2,6,6-Tetramethyl-1-octylpiperidine-4-spiro-2'-                             (1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-                               spiro-4"'-(2"',2"',6"',6"'-tetramethyl-1"'-octyl-                             piperidine)                                                              III-5)                                                                             1-Allyl-2,2,6,6-tetramethylpiperidine-4-spiro-2'-                             (1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-                               spiro-4"'-(1"'-allyl-2"',2"',6"',6"'-tetramethyl-                             piperidine)                                                              III-6)                                                                             1-Ethoxycarbonylmethyl-2,2,6,6-tetramethyl-                                   piperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-                               5'-(1",3"-dioxane)-2"-spiro-4"-(1"'-ethoxycarbonyl-                           methyl-2"',2"',6"',6"'-tetramethylpiperidine)                            III-7)                                                                             1-Benzyl-2,2,6,6-tetramethylpiperidine-4-spiro-                               2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-                            spiro-4"'-(1"'-benzyl-2"',2"',6"',6"'-tetramethyl-                            piperidine)                                                              III-8)                                                                             1-(2-Hydroxyethyl)-2,2,6,6-tetramethylpiperidine-                             4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1',3"-                                dioxane)-2"-spiro-4"'-[1"'-(2-hydroxyethyl)-2"',2"',                          6"',6"'-tetramethylpiperidine]                                           III-9)                                                                             1-(2-Acetoxyethyl)-2,2,6,6-tetramethylpiperidine-4-                           spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-                                  dioxane)-2"-spiro-4"'-[1"'-(2-acetoxyethyl)-2"',2"',6"',                      6"'-tetramethylpiperidine]                                               III-10)                                                                            1-(2-Acryloyloxyethyl)-2,2,6,6-tetramethylpiperidine-                         4-spiro-.sup.≠-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-             2"-spiro-4"'-[1"'-(2-acryloyloxyethyl)-2"',2"',6"',6"'-                       tetramethylpiperidine]                                                   III-11)                                                                            1-(2-Benzoyloxyethyl)-2,2,6,6-tetramethylpiperidine-                          4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-                                dioxane)-2"-spiro-4"'-(2-benzoyloxyethyl)-2"',                                2"',6"',6"'-tetramethylpiperidine]                                       III-12)                                                                            1-(2,3-Epoxypropyl)-2,2,6,6-tetramethylpiperidine-4-spiro-2'-                 (1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-[1'"-                (2,3-epoxypropyl)-2'",2'",6'",6'"-tetramethylpiperidine]                 III-13)                                                                            2,2,6,6-Tetramethyl-1-(2-stearoyloxyethyl)piperidine-                         4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-                    spiro-4"'-[2"',2"',6"',6"'-tetramethyl-1"'-(2-stearoyloxy-                    ethyl)piperidine]                                                        III-14)                                                                            2,2,6,6-Tetramethyl-1-methoxycarbonylmethylpiperidine-                        4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-                       2"-spiro-4"'-(2"',2"',6"',6"'-tetramethyl-1"'-                                methoxycarbonylmethylpiperidine)                                         __________________________________________________________________________

The compounds of the formula (IV).

    __________________________________________________________________________    IV-1)                                                                             8-Aza-2-hydroxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-                          spiro[4.5]decane                                                          IV-2)                                                                             8-Aza-2-hydroxymethyl-7,7,8,9,9-pentamethyl-1,4-dioxa-                        spiro[4.5]decane                                                          IV-3)                                                                             8-Aza-2-hydroxyethyl-7,7,9,9-tetramethyl-8-octyl-1,4-                         dioxa-spiro[4.5]decane                                                    IV-4)                                                                             8-Aza-8-(2-hydroxyethyl)-2-hydroxymethyl-7,7,9,9-                             tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-5)                                                                             8-Aza-8-benzyl-2-hydroxymethyl-7,7,9,9-tetramethyl-                           1,4-dioxa-spiro[4.5]decane                                                IV-6)                                                                             8-Aza-2-(2-hydroxyethyl)-7,7,9,9-tetramethyl-1,4-                             dioxa-spiro[4.5]decane                                                    IV-7)                                                                             8-Aza-2-(2-hydroxyethyl)-7,7,8,9,9-pentamethyl-1,4-                           dioxa-spiro[4.5]decane                                                    IV-8)                                                                             2-Acetoxymethyl-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-                          spiro[4.5]decane                                                          IV-9)                                                                             2-Acetoxymethyl-8-aza-7,7,8,9,9-pentamethyl-1,4-                              dioxa-spiro[4.5]decane                                                    IV-10)                                                                            8-Acetyl-8-aza-2-hydroxymetyl-7,7,9,9-tetramethyl-                            1,4-dioxa-spiro[4.5]decane                                                IV-11)                                                                            2-Acetoxymethyl-8-acetyl-8-aza-7,7,9,9-tetramethyl-                           1,4-dioxa-spiro[4.5]decane                                                IV-12)                                                                            2-Acetoxymethyl-8-acryloyl-8-aza-7,7,9,9-tetramethyl-                         1,4-dioxa-spiro[4.5]decane                                                IV-13)                                                                            2-Acetoxymethyl-8-aza-7,7,9,9-tetramethyl-8-octyl-                            1,4-dioxa-spiro[4.5]decane                                                IV-14)                                                                            2-Acetoxymethyl-8-allyl-8-aza-7,7,9,9-tetramethyl-                            1,4-dioxa-spiro[4.5]decane                                                IV-15)                                                                            2-Acetoxymethyl-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-                          8-(2-propynyl)-spiro[4.5]decane                                           IV-16)                                                                            2-Acetoxymethyl-8-aza-8-benzyl-7,7,9,9-tetramethyl-                           1,4-dioxa-spiro[4.5]decane                                                IV-17)                                                                            2-Acetoxymethyl-8-aza-8-ethoxycarbonylmethyl-7,7,9,9-                         tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-18)                                                                            2-Acetoxymethyl-8-aza-8-ethoxymethyl-7,7,9,9-                                 tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-19)                                                                            2-Acetoxymethyl-8-aza-8-(2,3-epoxypropyl)-7,7,9,9-                            tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-20)                                                                            8-Aza-2-(2,3-epoxypropyloxymethyl)-7,7,9,9-tetramethyl-                       1,4-dioxa-spiro[4.5]decane                                                IV-21)                                                                            2-Acetoxymethyl-8-aza-8-ethoxycarbonyl-7,7,9,9-                               tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-22)                                                                            2-Acetoxymethyl-8-aza-8-benzyloxycarbonyl-7,7,9,9-                            tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-23)                                                                            2-Acetoxymethyl-8-aza-8(2-chloroethyl)-7,7,9,9-                               tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-24)                                                                            2-Acetoxymethyl-8-aza-8-(2-hydroxyethyl)-7,7,9,9-                             tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-25)                                                                            2-Acetoxymethyl-8-(2-acetoxyethyl)-8-aza-7,7,9,9-                             tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-26)                                                                            2-Acetoxymethyl-8-aza-8-cyanomethyl-7,7,9,9-                                  tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-27)                                                                            8-Aza-2-butyryloxymethyl-7,7,9,9-tetramethyl-1,4-                             dioxa-spiro[4.5]decane                                                    IV-28)                                                                            8-Aza-2-decanoyloxymethyl-7,7,9,9-tetramethyl-1,4-                            dioxa-spiro[4.5]decane                                                    IV-29)                                                                            8-Aza-7,7,8,9,9-pentamethyl-1,4-dioxa-2-stearoyl-                             oxymethyl-spiro[4.5]decane                                                IV-30)                                                                            8-Acryloyl-2-acryloyloxymethyl-8-aza-7,7,9,9-                                 tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-31)                                                                            2-Acryloyloxymethyl-8-aza-7,7,8,9,9-pentamethyl-1,4-                          dioxa-spiro[4.5]decane                                                    IV-32)                                                                            8-Aza-2-methacryloxyloymethyl-7,7,8,9,9-pentamethyl-                          1,4-dioxa-spiro[4.5]decane                                                IV-33)                                                                            8-Aza-2-crotonoyl-1,4-dioxa-7,7,8,9,9-pentamethyl-                            oxymethyl-spiro[4.5]decane                                                IV-34)                                                                            8-Aza-2-benzoyloxymethyl-7,7,9,9-tetramethyl-1,4-                             dioxa-spiro[4.5]decane                                                    IV-35)                                                                            8-Aza-2-benzoyloxymethyl-7,7,8,9,9-pentamethyl-                               1,4-dioxa-spiro[4.5]decane                                                IV-36)                                                                        IV-37)                                                                            8-Aza-8-(2-benzoyloxyethyl)-2-benzoyloxymethyl-7,7,9,9-                       tetramethyl-1,4-dioxa-spiro[4.5]decane                                    IV-38)                                                                            8-Aza-2-(p-t-butylbenzoyloxymethyl)-7,7,8,9,9-pentamethyl-                    1,4-dioxa-spiro[4.5]decane                                                IV-39)                                                                            8-Aza-2-[β-(3,5-di-t-butyl-4-hydroxyphenyl)-                             propionyloxymethyl]-7,7,8,9,9-pentamethyl-1,4-dioxa-                          spiro[4.5]decane                                                          IV-40)                                                                            8-Aza-7,7,8,9,9-pentamethyl-1,4-dioxa-2-salicyloyl-                           oxymethyl-spiro[4.5]decane                                                IV-41)                                                                            8-Aza-8-benzyl-7,7,9,9-tetramethyl-2-(m-toluoyloxy-                           methyl)-1,4-dioxa-spiro[4.5]decane                                        IV-42)                                                                            8-Aza-2(p-chlorobenzoyloxymethyl)-7,7,9,9-tetramethyl-                        1,4-dioxa-spiro[4.5]decane                                                IV-43)                                                                            8-Aza-2-(p-chlorobenzoyloxymethyl)-7,7,9,9-tetramethyl-                       1,4-dioxa-8-(2-propynyl)-spiro[4.5]decane                                 IV-44)                                                                            2-(o-Anisoyloxymethyl)-8-aza-7,7,9,9-tetramethyl-                             1,4-dioxa-spiro[4.5]decane                                                IV-45)                                                                            2-(o-Anisolyloxymethyl)-8-aza-7,7,8,9,9-pentamethyl-                          1,4-dioxa-spiro[4.5]decane                                                IV-46)                                                                            8-Aza-7,7,8,9,9-pentamethyl-2-(β-naphthoyloxymethyl)-                    1,4-dioxa-spiro[4.5]decane                                                IV-47)                                                                            8-Aza-7,7,8,9,9-pentamethyl-2-(β-octylthio-                              propionyloxymethyl)-1,4-dioxa-spiro[4.5]decane                            IV-48)                                                                            8-Aza-2-(2-furoyloxymethyl)-7,7,8,9,9-pentamethyl-                            1,4-dioxa-spiro[4.5]decane                                                IV-49)                                                                            8-Aza-2-isonicotinoyloxymethyl-7,7,8,9,9-pentamethyl-                         1,4-dioxa-spiro[4.5]decane                                                IV-50)                                                                            8-Aza-2-benzenesulfinyloxymethyl-7,7,8,9,9-pentamethyl-                       1,4-dioxa-spiro[4.5]decane                                                IV-51)                                                                            8-Aza-2-mesyloxymethyl-7,7,8,9,9-pentamethyl-1,4-                             dioxa-spiro[4.5]decane                                                    IV-52)                                                                            8-Aza-7,7,8,9,9-pentamethyl-1,4-dioxa-2-tosyloxy-                             methyl-spiro[4.5]decane                                                   IV-53)                                                                            8-Aza-2-ethylcarbamoyloxymethyl-7,7,8,9,9-pentamethyl-                        1,4-dioxa-spiro[4.5]decane                                                IV-54)                                                                            8-Aza-7,7,8,9,9-pentamethyl-1,4-dioxa-2-phenyl-                               carbamoyloxymethyl-spiro[4.5]decane                                       IV-55)                                                                            8-Aza-2-cyclohexylthiocarbamoyloxymethyl-7,7,8,9,9-                           pentamethyl-1,4-dioxa-spiro[4.5]decane                                    IV-56)                                                                            8-Aza-2-methoxymethyl-7,7,9,9-tetramethyl-1,4-                                dioxa-spiro[4.5]decane                                                    IV-57)                                                                            8-Aza-7,7,8,9,9-pentametyl-1,4-dioxa-2-octyloxy-                              methyl-spiro[4.5]decane                                                   IV-58)                                                                            8-Aza-7,7,8,9,9-pentamethyl-1,4-dioxa-2-stearyl                               oxymethyl-spiro[4.5]decane                                                IV-59)                                                                            2-Allyloxymethyl-8-aza-7,7,9,9-tetramethyl-1,4-                               dioxa-spiro[4.5]decane                                                    IV-60)                                                                            2-Allyloxymethyl-8-aza-7,7,8,9,9-pentamethyl-1,4-                             dioxa-spiro[4.5]decane                                                    IV-61)                                                                            8-Aza-7,7,8,9,9-pentamethyl-1,4-dioxa-2-(2-propynyl-                          oxymethyl)-spiro[4.5]decane                                               IV-62)                                                                            8-Aza-2-benzyloxymethyl-7,7,9,9-tetramethyl-1,4-                              dioxa-spiro[4.5]decane                                                    IV-63)                                                                            8-Aza-2-ethoxymethoxymethyl-7,7,8,9,9-pentamethyl-                            1,4-dioxa-spiro[4.5]decane                                                IV-64)                                                                            8-Aza-2-(β-ethoxycarbonylvinyloxymethyl)-7,7,8,9,9-                      pentamethyl-1,4-dioxa-spiro[4.5]decane                                    IV-65)                                                                            8-Aza-2-(α-methyl-β-methoxycarbonylvinyloxymethyl)-                7,7,8,9,9-pentamethyl-1,4-dioxa-spiro[4.5]decane                          IV-66)                                                                            8-Aza-7,7,8,9,9-pentamethyl-2-(α-methyl-β-octyloxy-                carbonylvinyloxymethyl)-1,4-dioxa-sprio[4.5]decane                        IV-67)                                                                            8-Aza-7,7,8,9,9-pentamethyl-1,4-dioxa-2-phenoxymethyl-                        spiro[4.5]decane                                                          IV-68)                                                                            8-Aza-2-(2,3-epoxypropyloxymethyl)-7,7,8,9,9-                                 pentamethyl-1,4-dioxa-spiro[4.5]decane                                    IV-69)                                                                            8-Aza-2-(3-methoxysulfonylpropyloxymethyl)-7,7,8,9,9-                         pentametyl-1,4-dioxa-spiro[4.5]decane                                     IV-70)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                              [4.5]-2-decylmethyl)carbonate                                             IV-71)                                                                            Bis(8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]-                           2-decylmethyl)succinate                                                   IV-72)                                                                            Bis(8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]-                           2-decylmethyl)adipate                                                     IV-73)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro[4.5]-                         2-decylmethyl)adipate                                                     IV-74)                                                                            Bis(8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]-                           2-decylmethyl)sebacate                                                    IV-75)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                              [4.5]-2-decylmethyl)sebacate                                              IV-76)                                                                            Bis(8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]-                           2-decylmethyl)terephthalate                                               IV-77)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                              [4.5]-2-decylmethyl)terephthalate                                         IV-78)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                              [4.5]-2-decylmethyl)thiodipropionate                                      IV-79)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                              [4.5]-2-decylmethyl)sulfite                                               IV-80)                                                                            1,2-Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                          [4.5]-2-decylmethoxy)ethane                                               IV-81)                                                                            1,4-Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                          [4.5]-2-decylmethoxy)-2-butene                                            IV-82)                                                                            1,4-Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                          [4.5]-2-decylmethoxy)-2-butyne                                            IV-83)                                                                            α,α'-Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-                   spiro[4.5]-2-decylmethoxy)-p-xylene                                       IV-84)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                              [4.5]-2-decylmethyl)hexamethylene-1,6-dicarbamate                         IV-85)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                              [4.5]-2-decylmethyl)toluene-2,4-dicarbamate                               IV-86)                                                                            Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                              [4.5]-2-decylmethyl)diphenylmethane-p-p'-dicarbamate                      IV-87)                                                                            Tris(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                             [4.5]-2-decylmethyl)trimesate                                             IV-88)                                                                            Tris(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro-                             [4.5]-2-decylmethyl)phosphite                                             IV-89)                                                                            Tetrakis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-                               spiro[4.5]-2-decylmethyl)pyromellitate                                    IV-90)                                                                            8-Aza-7,7,9,9-tetramethyl-2-stearoyloxymethyl-1,4-                            dioxa-spiro[4.5]decane                                                    IV-91)                                                                            8-Aza-7,7,9,9-tetramethyl-2-(m-toluoyloxymethyl)-1,4-                         dioxa-spiro[4.5]decane                                                    IV-92)                                                                            8-Aza-7,7,9,9-tetramethyl-2-salicyloyloxymethyl)-                             1,4-dioxa-spiro[4.5]decane                                                __________________________________________________________________________

The compounds of the formula (V),

    ______________________________________                                        V-1)  Cis-2,4,7-trioxabicyclo[3.3.0]octane-3-spiro-4'-                              (2',2',6',6'-tetramethylpiperidine)                                     V-2)  Cis-2,4,7-trioxabicyclo[3.3.0]octane-3-spiro-4'-                              (1',2',2',6'6,'-pentamethylpiperidine)                                  V-3)  Cis-2,4,7-trioxabicyclo[3.3.0]octane-3-spiro-4'-                              (1'-acetyl-2',2',6',6'-tetramethylpiperidine)                           ______________________________________                                    

In this invention, the following are included as preferred compounds.

a. Compounds having the aforementioned formula (II) wherein R₁ ishydrogen atom or methyl group, n, is 1 or 2, R₂ is, when n is 1, asaturated aliphatic acyl group having carbon atoms of 2-18 or benzoylgroup which may be substituted with alkyl of C₁ -C₄ or hydroxy,preferably benzoyl or salicyloyl and, when n, is 2, a saturatedaliphatic diacyl group having carbon atoms of 4-12 or terephthaloylgroup, and R₅ ' is methyl group or ethyl group.

b. Compounds having the aforementioned formula (III) wherein R₁ and R₆are hydrogen atom, methyl group or allyl group.

c. Compounds having the aforementioned formula (IV) wherein R₁ ishydrogen atom or methyl group, m is 1, n is 1 or 2, and R₂ is, when n is1, a saturated aliphatic acyl group having carbon atoms of 2-18 orbenzoyl group which may be substituted with alkyl of C₁ -C₄ or hydroxy,preferably benzoyl or salicylolyl and, when n is 2, a saturatedaliphatic diacyl group having carbon atoms of 4-12 or terephthaloyl,

The compounds of this invention may be prepared, for instances, asstated below, but the procedures per se may be effected in a well-knownmanner.

1. The compounds (II-1), (III-1), (IV) and (V) can be prepared byreacting the triacetoamine derivatives (VI) with the trimethylolderivatives (VII), pentaerythrite) (VIII), the glycerin derivatives (IX)and the mesoerythritol derivatives (X), respectively, in the presence ofan acidic catalyst such as p-toluenesulfonic acid, sulfuric acid orhydrochloric acid in the presence or absence of a solvent with heating.##STR14##

In the above formulae, R₁, R₂, R'₅, n and m are as defined above.

2. Introduction of such groups as acyl group, alkyl group and the likeinto the hydroxyl group or the amine may be conducted by reacting with ahalide in the presence of an acid-binding agent. In general, where thehalide is employed in a small amount, the compound having thesubstituent introduced to the hydroxyl group is obtained, whereas thecompound having the substituents introduced to the hydroxyl group andamine if used in an excess amount. As the acid-binding agent may beemployed inorganic or organic basic substances such as sodium iodide,potassium carbonate, sodium hydroxide, sodium hydride, triethylamine,sodium alcoholate, potassium p-toluenesulfonate or sodium acetate.Alternatively, the introduction of acyl group may be effected through areaction with an acid anhydride or an ester interchange reaction with anacid ester, instead of the above reaction with a halide. ##STR15##

In the above formulae, R₁ and n are as defined above, R'₂ representsother group than hydrogen atom, N-substituted carbamoyl group,N-substituted thiocarbamoyl group or N-substituted dicarbamoyl group inthe above R₂ and X represents halogen atom. ##STR16##

In the above formulae, A and n are as defined above, R'₁ representsother group than hydrogen atom in the above R₁ R"₂ represents othergroup than hydrogen atom in the above R₂ and X represents halogen atom.

3. Introduction of the N-substituted carbamoyl group, N-substitutedthiocarbamoyl group into the hydroxyl group may be conducted through areaction with a substituted isocyanic acid or a substitutedisothiocyanic acid in the presence of an acid binding agent. ##STR17##

In the above formulae, A and R₁ are as defined above, Y representsoxygen or sulfur atom, R'"₂ represents a substituent on the carbamoylgroup or thiocarbamoyl group.

In this invention, the piperidine derivatives (I) employed as astabilizer may be easily incorporated (I) employed as a stabilizer maybe easily incorporated into a synthetic polymeric material by variousmethods commonly used in the art. The stabilizer may be added to asynthetic polymeric material at any stage in the manufacture of a moldedproduct therefrom. For example the stabilizer of a dry powder may beadmixed with a synthetic polymeric material or a suspension or emulsionof the stabilizer may be admixed therewith.

The amount of the piperidine derivative (I) which may be added to asynthetic polymeric material according to this invention is varied uponthe kind, nature and purpose for use of the synthetic polymeric materialto be added. In general, the amount ranging in 0.01-5% by weight may beemployed to the weight of a synthetic polymeric material, but apractical range may be varied upon the synthetic polymeric material andthere may be used 0.01-2.0% by weight, desirably 0.02-1.0% by weight forpolyolefin; 0.01-1.0% by weight, desirably 0.02-0.5% by weight forpolyvinyl chloride and polyvinylidene chloride; 0.01-5.0% by weight,desirably 0.02-2.0% by weight for polyurethane and polyamide.

The compounds according to the formulae (II) and (IV) of the presentinvention are excellent in compatibility in polymeric materials,especially polyolefin.

The above-mentioned stabilizer may be used alone or in admixture withknown additives such as antioxidants, ultraviolet absorbents, fillers,pigments and the like. The additives are exemplified by the following.

Antioxidants

Simple 2,6-dialkylphenols, such as, for example2,6-di-tert.butyl-4-methylphenol, 2-tert.butyl-4,6-dimethylphenol,2,6-di-tert.butyl-4-methoxymethylphenol and2,6-dioctadecyl-4-methylphenol.

Derivatives of alkylated hydroquinones, such as, for example2,5-di-tert.butyl-hydroquinone, 2,5-di-tert.amyl-hydroquinone,2,6-di-tert.butyl-hydroquinone, 2,5-di-tert.butyl-4-hydroxyanisole,3,5-di-ter.butyl-4-hydroxyanisole andtris(3,5-di-tert.butyl-4-hydroxyphenyl)phosphite,3,5-di-tert.butyl-4-hydroxyphenylstearate,di-(3,5-di-tert.butyl-4-hydroxyphenyl)adipate.

Hydroxylated thiodiphenyl ethers, such as, for example,2,2'-thiobis(6-tert.butyl-4-methylphenol), 2,2'-thiobis-(4-octylphenol),4,4'-thiobis(6-tert.butyl-3-methylphenol),4,4'-thiobis(3,6-di-sec.amylphenol) and 4,4'-thiobis(6-tert.butyl-2-methylphenol),4,4'-Bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

Alkylidene-bisphenols, such as, for example,2,2'-methylene-bis(6-tert.butyl-4-methylphenol),2,2'-methylene-bis(6-tert.butyl-4-ethylphenol),4,4'-methylenebis(6-tert.butyl-2-methylphenol),4,4'-methylene-bis-(2,6-di-tert.butylphenol),2,6-di(3-tert.butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,2,2'-methylene-bis[4-methyl-6-(α-methylcyclohexyl)-phenol],1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-butane,1,1-bis(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane,2,2-bis(5-tert.butyl-4-hydroxy-2-methylphenyl)butane,2,2-bis(3,5-di-tert.butyl-4-hydroxyphenyl)propane,1,1,3-tris-(5-tert.butyl-4-hydroxy-2-methylphenyl)butane,2,2-bis(5-tert.butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert.butyl-4-hydroxy-2-methylphenyl)pentane and ethyleneglycol bis[3,3-bis(3'-tert.butyl-4'-hydroxyphenyl)butyrate].

O-, n- and S-benzyl compounds, such as for example,3,5,3',5'-tetra-tert.butyl-4,4'-dihydroxydibenzylether,4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic acid octadecyl ester,tri(3,5-di-tert.butyl-4-hydroxybenzyl)amine, andbis(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate.

Hydroxybenzylated malonic esters, such as, for example,2,2-bis(3,5-di-tert.butyl-2-hydroxybenzyl)malonic acid dioctadecylester, 2-(3-tert.butyl-4-hydroxy-5-methylbenzyl)malonic acid dioctadecylester, 2,2-bis(3,5-di-tert.butyl-4-hydroxybenzyl)malonic aciddi-dodecylmercaptoethyl ester and,2,2-bis(3,5-di-tert.butyl-4-hydroxybenzyl)malonic aciddi(4-tert.octylphenyl)ester.

Hydroxybenzyl-aromatics, such as, for example,1,3,5-tri(3,5-di-tert.butyl-4-hydroxybenzyl)-2,4,6-tri-methylbenzene,1,4-di(3,5-di-tert.butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and2,4,6-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)phenol.

s-Triazine compounds, such as, for example,2,4-bis-octylmercapto-6-(3,5-di-tert.butyl-4-hydroxyanilino)-s-triazine,2-octylmercapto-4,6-bis(3,5-di-tert.butyl-4-hydroxyanilino)-s-triazine,2-octylmercapto-4,6-bis(3,5-di-tert.butyl-4-hydroxyphenoxy)-s-triaxine,2,4,6-tris(3,5-ditert.butyl-4-hydroxyphenoxy)-s-triazine,2,4,6-tris(3,5-di-tert.butyl-4-hydroxyphenylethyl)-s-triazine and1,3,6-tris-(3,5-di-ter.-butyl-4-hydroxybenzyl)isocyanurate.

Amides of 3,5-di-tert.butyl-4-hydroxyphenylpropionic acid, such as, forexample,1,3,5-tris(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazineandN,N'-bis(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)hexamethylenediamine.

Esters of 3,5-di-tert.butyl-4-hydroxyphenylpropionic acid withmonohydric or polyhydric alcohols, such as, for example, methanol,ethanol, octadecanol, 1,6-hexanediol; 1,9-nonanediol, ethylene glycol,1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol,trimethylhexanediol, trimethylolethane, trimethylolpropane,tris-hydroxyethyl-isocyanurate and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

Esters of 5-tert.butyl-4-hydroxy-3-methylphenylpropionic acid withmonohydric or polyhydric alcohols, such as, for example, methanol,ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol,trimethylhexanediol, trimethylolethane, trimethylolpropane,tris-hydroxyethylisocyanurate and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane.

Esters of 3,5-di-tert.butyl-4-hydroxyphenylacetic acid with monohydricor polyhydric alcohols, such as, for example, methanol, ethanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolethane, trimethylolpropane,tris-hydroxyethyl-isocyanurate and4-hydroxymethyl-1-phospha-2,6,7-tri-oxabicyclo[2,2,2]octane.

Acylaminophenols, such as, for example,N-(3,5-di-tert.-butyl-4-hydroxyphenyl)stearic acid amide andN,N'-bis-(3,5-di-tert.butyl-4-hydroxyphenyl)-thio-bis-acetamide.

benzylphosphonates, such as, for example,3,5-di-tert.-butyl-4-hydroxybenzylphosphonic acid di-methyl ester,3,5-di-tert.butyl-4-hydroxybenzylphosphonic acid diethyl ester,3,5-di-tert.butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester and5-tert.butyl-4-hydroxy-3-methylbenzylphosphonic acid dioctadecyl ester.

Aminoaryl derivatives, such as, for example, phenyl-1-naphthylamine,phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylenediamine,N,N'-di-2-naphthyl-p-phenylenediamine,N,N'-di-sec,butyl-p-phenylenediamine,6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline,6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, mono- anddi-octyliminodibenzyl and polymerised2,2,4-trimethyl-1,2-dihydroquinoline.

UV-absorbers and light protection agents

2-(2'-Hydroxyphenyl)-benztriazoles, such as, for example, the5'-methyl-, 3',5'-di-tert.butyl-, 5'-tert.butyl-,5'-(1,1,3,3-tetramethyl-butyl)-, 5-chloro-3',5'-di-tert.butyl-,5-chloro-3'-tert.butyl-5'-methyl-, 3'-sec.butyl-5'-tert.butyl-,3'-[α-methylbenzyl]-5'-methyl-, 3'-[α-methylbenzyl]-5'-methyl-5-chloro-,4'-hydroxy-, 4'-methoxy-, 4'-octoxy-, 3',5'-di-tert.amyl-,3'-methyl-5'-carbomethoxyethyl-,5-chloro-3',5'-di-tert.amyl-derivatives.

2,4-Bis(2'-hydroxyphenyl)-6-alkyl-s-triazines, such as, for example, the6-ethyl-, 6-undecyl- or 6-heptadecylderivatives.

2-Hydroxy-benzophenones, such as, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-,4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxy-derivatives.

1,3-Bis(2'-hydroxy-benzoyl)benzenes, such as, for example,1,3-bis(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene,1,3-bis(2'-hydroxy-4'-octoxy-benzoyl)-benzene,1,3-bis(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene.

Esters of optionally substituted benzoic acids, such as, for example,phenyl salicylate, octylphenyl salicylate, di-benzoylresorcinol,bis(4-tert.butylbenzoyl)resorcinol, benzoyl-resorcinol,3,5-di-tert.butyl-4-hydroxybenzoic acid 2,4-di-tert.butylphenyl ester,octadecyl ester or 2-methyl-4,6-di-tert.butylphenyl ester.

Acrylates, such as, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxycinnamic acid methyl ester,α-cyano-β-methyl-p-methoxycinnamic acid methyl ester or butyl ester andN-(β-carbomethoxy-vinyl)-2-methylindoline.

Nickel compounds, such as, for example, nickel complexes of2,2'-thiobis(4-tert.octylphenol), such as the 1:1 and 1:2 complex,optionally with other ligands such as n-butylamine, triethanolamine, orN-cyclohexyl-diethanolamine, nickel complexes ofbis(4-tert.octylphenyl)-sulphone, such as the 2:1 complex, optionallywith other ligands such as 2-ethyl-caproic acid, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert.-butylbenzylphosphonic acid monoalkyl esters, suchas the methyl, ethyl or butyl ester, the nickel complex of2-hydroxy-4-methyl-phenyl-undecyl-ketonoxime and nickel3,5-di-tert.butyl-4-hydroxybenzoate.

Oxalic acid diamides, such as, for example, 4,4'-dioctyloxyoxanilide,2,2'-dioctyloxy-5,5'-di-tert.butyloxanilide,2,2'-di-dodecyloxy-5,5'-di-tert.butyloxanilide,2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide,N,N'-bis-(3-dimethylaminopropyl)oxalamide, mixtures of o- and p-methoxyand o- and p-ethoxy-di-substituted oxanilides and mixtures of2-ethoxy-5-tert.butyl-2'-ethyloxanilide with2-ethoxy-2'-ethyl-5,4'-di-tert.butyloxanilide.

Metal deactivators, such as, for example, oxanilide, isophthalic aciddihydrazide, sebacic acid bis-phenylhydrazide, bis-benzylidene oxalicacid di-hydrazide, N,N'-diacetyl-adipic acid dihydrazide,N,N'-bis-sali-cycloyloxalic acid dihydrazide,N,N'-bis-salicyloyl-hydrazine andN,N'-bis-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hydrazine.

Phosphites, such as, for example triphenylphosphite, diphenylalkyl-phosphites, phenyl dialkylphosphites, trinonylphenylphosphite,trilaurylphosphite, trioctadecylphosphite,3,9-di-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphospha-spiro[5.5]undecaneand tris(4-hydroxy-3,5-di-tert.butylphenyl)phosphite.

Compounds which destroy peroxide, such as, for example esters ofβ-thiodipropionic acid, e.g., the lauryl, stearyl, myristyl or tridecylester, salts of 2-mercaptobenzimidazole, e.g., the zinc salt, anddiphenylthiourea.

Polyamide stabilizers, such as, for example, copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

Basic co-stabilizers, such as, for example, polyvinylpyrrolidone,melamine, benzoguanamine, triallyl cyanurate, dicyandiamide, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanesand alkali metal salts and alkaline earth metal salts of highersaturated or unsaturated fatty acids, e.g., Ca stearate, Mg laurate, Naricinoleate, K palmitate and Zn stearate.

Pvc stabilizers, such as, for example, organic tin compounds, organiclead compounds and Ba/Cd salts of fatty acids.

Nucleating agents, such as, for example, 4-tert.butyl-benzoic acid,adipic acid and diphenylacetic acid.

Other additives, such as, for example, plasticizers, lubricants, e.g.,glycerine monostearate, emulsifiers, antistatic agents, flameproofingagents, pigments, carbon black, asbestos, glass fibres, kaolin and talc.

Other additive such as these may be usually blended into the piperidinederivative (I) of this invention and advantageously employed at a ratioof 0.5-3 parts to 1 part.

Examples 1 to 8 describe the synthetic polymeric material compositionshaving incorporated therein the piperidine derivative (I) and theirstabilizing effects and Referential Examples 1 to 14 describe thepreparation of the piperidine derivative (I).

Example 1

Into 100 parts of polypropylene ["Noblen JHH-G", trade name, after twicerecrystallizations from monochlorobenzene, available from Mitsui ToatsuChemicals Inc.] was incorporated 0.25 part of the stabilizer of thisinvention. The resulting mixture was blended and molten. The moltenmixture was molded into a sheet with a thickness of 0.5 mm. underheating and pressure.

The sheet was exposed to irradiation of ultraviolet ray at 45° C in aFade-Meter and the time when the sheet becomes brittle was measured.

The results are shown in Table 1.

Example 2

Into 100 parts of high-density polyethylene ["Hi-Zex", trade name,available from Mitsui Toatsu Chemicals Inc., after twicerecrystallizations from toluene] was incorporated 0.25 part of thestabilizer of this invention. The resulting mixture was blended andmolten and molded into a sheet with a thickness of 0.5 mm. under heatingand pressure.

The sheet was exposed to irradiation of ultraviolet ray at 45° C in aFade-Meter and the time when the sheet becomes brittle was measured.

The results are given in Table 1. The Nos. of stabilizers recitedhereinafter are referred to hereinbefore.

                  Table 1                                                         ______________________________________                                        Stabilizer                High-density                                        No.         Polypropylene Polyethylene                                        ______________________________________                                        II-2          620 hours    1280 hours                                         II-3          700          1460                                               II-4          680          1440                                               II-5          760          1580                                               II-7          880          1760                                               II-8          820          1640                                               II-10         860          1920                                               II-14         720          1700                                               II-15         880          1820                                               II-20         640          1180                                               II-21         680          1420                                               II-22         660          1260                                               II-25         820          1780                                               II-28         840          1880                                               II-30         700          1620                                               II-32         860          1760                                               II-33         880          1940                                               II-40         500           940                                               II-44         580          1060                                               II-50         620          1160                                               II-51         720          1480                                               II-56         840          1620                                               II-57         880          1680                                               II-59         820          1760                                               II-72         680          1240                                               II-73         560          1160                                               II-74         460          1080                                               II-75         920          1480                                               II-76         920          1700                                               II-77         900          1520                                               II-78         880          1640                                               II-79         900          1820                                               II-80         880          1500                                               II-81         740          1460                                               II-82         900          1780                                               III-1         720          1540                                               III-2         780          1640                                               III-3         820          1780                                               III-4         800          1720                                               III-7         780          1680                                               III-8         760          1620                                               III-9         840          1760                                               III-10        880          1880                                               III-11        900          1880                                               III-12        940          1960                                               IV-1          620          1300                                               IV-2          660          1380                                               IV-4          720          1580                                               IV-5          680          1520                                               IV-8          640          1480                                               IV-9          800          1780                                               IV-10         580          1220                                               IV-11         640          1360                                               IV-14         720          1560                                               IV-16         720          1520                                               IV-17         740          1600                                               IV-19         860          1840                                               IV-20         760          1640                                               IV-24         620          1100                                               IV-25         800          1740                                               IV-26         760          1600                                               IV-27         600          1220                                               IV-28         780          1720                                               IV-37         720          1440                                               IV-40         780          1780                                               IV-41         700          1620                                               IV-42         720          1600                                               IV-43         600          1480                                               IV-44         740          1780                                               IV-45         800          1820                                               IV-53         620          1240                                               IV-54         680          1440                                               IV-56         640          1280                                               IV-59         700          1340                                               IV-60         780          1520                                               IV-62         640          1320                                               IV-71         800          1860                                               IV-72         880          2020                                               IV-74         940          2200                                               IV-76         740          1700                                               IV-77         640          1420                                               IV-90         580          1360                                               IV-91         560          1480                                               IV-92         700          1680                                               V-1           620          1380                                               V-2           640          1420                                               Tinuvin 327*  300          640                                                None          60           380                                                ______________________________________                                         *Tinuvin 327: 2-(2-hydroxy-3,5-di-tert-butylphenyl)-6-chloro-1,2,3-triazo                                                                              

Example 3

Into 100 parts of polystyrene ["Styron", trade name, afterrecrystallization from a mixture of benzene with methanol, availablefrom Asahi-Dow Limited.] was incorporated 0.25 part of the stabilizer ofthis invention. The resulting mixture was molded at 180° C underpressure into a plate with a thickness of 1 mm.

The plate thus formed was subjected to the exposure of ultraviolet rayirradiation in a Fade-Meter at 45° C for 500 hours. A test piece of thetreated plate was tested for color-difference by means of acolor-difference colorimeter according to the method prescribed inJapanese Industrial Standard "K-7103", and a change of the yellownessindex of the plate was calculated according to the following equation:

    ΔYI = YI - YI.sub.0

wherein ΔYI means a change of yellowness index, YI means a yellownessindex after exposure and YI₀ means an initial yellowness index of a testpiece.

The results are shown in Table 2.

                  Table 2                                                         ______________________________________                                        Stabilizer No.                                                                             YI.sub.O      ΔYI                                          ______________________________________                                        II-8         4.8           +2.7                                               II-59        4.7           +2.8                                               II-76        4.0           +2.0                                               II-77        3.9           +2.3                                               III-1        4.9           +3.2                                               III-7        4.1           +2.1                                               III-11       3.9           +2.3                                               IV-1         4.6           +3.3                                               IV-9         4.5           +2.7                                               IV-25        4.5           +3.0                                               IV-45        3.8           +2.3                                               IV-76        4.1           +3.1                                               IV-80        4.3           +4.2                                               IV-82        4.1           +3.8                                               Tinuvin P*   4.9           +4.7                                               ______________________________________                                        None         4.7            +16.3                                             ______________________________________                                         *Tinuvin P: 2-(2-hydroxy-5-methyl)benzo-1,2,3-triazol                    

Example 4

Into 100 parts of ABS resin ["Kane Ace B-12", trade name, available fromKanegafuchi Chemical Industries, Co., Ltd.] was incorporated 0.5 part ofthe stabilizer of this invention, the resulting mixture was kneaded on akneading roll at 160° C for 6 minutes and then molded into a sheet witha thickness of about 0.5 mm.

The sheet was treated in a sunshine weather-ometer for 50 hours andtested for retentions of ultimate elongation and of ultimate tensilestrength as well as coloration degree were determined by a conventionalmethod. The results are shown in Table 3.

                  Table 3                                                         ______________________________________                                        Stabilizer    Retention of                                                                             Retention of                                         No.           elongation tensile strength                                     ______________________________________                                        II-5           69%        76%                                                 II-59          73%        81%                                                 III-10        72         79                                                   III-12        77         82                                                   IV-9          74         75                                                   IV-41         75         79                                                   IV-72         77         80                                                   ______________________________________                                        None          53         69                                                   ______________________________________                                    

Example 5

Into 100 parts of 6-nylon resin ["CM1011", trade name, availabel fromToray Industries Inc.] was incorporated 0.25 part of the stabilizer ofthis invention. The resulting mixture was heated and melted and thenmolded into a film having a thickness of about 0.1 mm. under pressure bya conventional compression molding machine. The film thus formed wasaged under the following aging condition and thereafter subjected to atensile test to determine the retentions of tensile strength andelongation.

Aging conditions

1. Exposure to ultraviolet ray for 200 hours in a Fade-Meter at 45° C.

2. Aging at 160° C for 2 hours in a Geer's aging tester. The results areshown in Table 4.

                  Table 4                                                         ______________________________________                                               Fade-meter    Geer's aging tester                                                         Retention         Retention                                         Retention of        Retention                                                                             of                                       Stabilizer                                                                             of        tensile   of      tensile                                  No.      elongation                                                                              strength  elongation                                                                            strength                                 ______________________________________                                        II-8      69%       72%       71%     68%                                     II-59     73%       82%       72%     80%                                     III-1    72        74        70      72                                       III-7    69        71        71      70                                       III-12   78        84        76      82                                       IV-17    68        70        73      70                                       IV-26    71        75        75      71                                       IV-76    76        78        78      73                                       ______________________________________                                        None     19        50        18      53                                       ______________________________________                                    

Example 6

Into 100 parts of polycaprolactone type polyurethane ["E-5080", tradename, available from The Nippon Elastollan Industries Ltd.] wasincorporated 0.5 part of the stabilizer of this invention. The resultingmixture was heated and melted and then molded into a sheet having athickness of about 0.5 mm. The sheet thus formed was subjected to theexposure to ultraviolet ray in a Fade-Meter at 45° C for 15 hours andthen tested for the retentions of elongation and tensile strength.

The results are shown in Table 5.

                  Table 5                                                         ______________________________________                                        Stabilizer    Retention of                                                                             Retention of                                         No.           elongation tensile strength                                     ______________________________________                                        II-5           86%        91%                                                 III-4         91         93                                                   III-11        96         96                                                   IV-1          83         87                                                   IV-17         85         90                                                   IV-26         88         91                                                   IV-76         90         93                                                   ______________________________________                                        None          74         52                                                   ______________________________________                                    

Example 7

Into 100 parts of polyvinyl chloride ["Geon 103EP", trade name,available from The Nippon Zeon Co., Ltd.] were incorporated 3 parts ofbutyl tin maleate, 0.5 part of butyl stearate and 0.25 part of thestabilizer of this invention and the resulting mixture was kneaded for 5minutes on a kneading roll at 180° C and formed into a sheet with athickness of 0.5 mm. The sheet was treated in a sunshine weather-ometerfor 300 hours and then the discoloration thereof was observed.

The results are shown in Table 6.

                  Table 6                                                         ______________________________________                                        Stabilizer No.  Discoloration                                                 ______________________________________                                        II-5            Pale brown                                                    III-7           "                                                             III-12          "                                                             IV-2            "                                                             IV-11           "                                                             IV-19           Orange-yellow                                                 IV-45           Pale brown                                                    IV-72           "                                                             ______________________________________                                        None            Dark brown                                                    ______________________________________                                    

Example 8

Into 100 parts of polyester resin ["Ester-C13", trade name, availablefrom Mitsui Toatsu Chemicals, Inc.] were incorporated 1 part of benzoylperoxide and 0.2 part of the stabilizer. The resulting mixture was curedby pre-heating at 60° C for 30 minutes and then heating at 100° C foradditional 1 hour to be formed into a plate with a thickness of 3 mm.

The plate thus formed was exposed to irradiation in the sunshineweather-ometer for 60 hours and the change of yellowness index thereofwas determined according to the same method as described in the aboveExample 3.

The results are shown in Table 7.

                  Table 7                                                         ______________________________________                                        Stabilizer No.    YI.sub.o                                                                              ΔYI                                           ______________________________________                                        II-8              2.2     +7.7                                                III-1             2.3     +6.9                                                III-11            2.3     +6.8                                                III-12            2.5     +7.3                                                IV-9              2.5     +8.0                                                IV-16             2.3     +8.2                                                IV-45             2.2     +7.9                                                IV-72             2.3     +7.7                                                ______________________________________                                        None              1.8     +13.1                                               ______________________________________                                    

REFERENTIAL EXAMPLE 19-Aza-3-hydroxymethyl-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane(Illustrated compound II-2)

To 32.7 g. of p-toluenesulfonate of triacetonamine were added 12 g. oftrimethylolethane, 1.5 g. of p-toluenesulfonic acid and 200 ml. oftoluene and reflux with heating was conducted for 5 hours while thewater formed was removed. After cooling, neutralization was made by theaddition of an 30% aqueous solution of sodium hydroxide and separationof liquids was effected to recover a toluene layer, which was thenwashed with water, dried and concentrated under reduced pressure.Residual crystals were recrystallized from a mixed liquid of 1:1 ofbenzene-petroleum ether to give the end product as white crystalsmelting at 125°-126° C.

Analysis for C₁₄ H₂₇ NO₃ :

Calculated: C, 65.33%; H, 10.57%; N, 5.41%.

Found: C, 65.12%; H, 10.47%; N, 5.47%.

REFERENTIAL EXAMPLE 29-Aza-3-ethyl-3-hydroxymethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane(Illustrated compound II-21)

In the substantially same manner as shown in the Referential Example 1,32.7 g. of p-toluenesulfonate of triacetonamine, 13.4 g. oftrimethylolpropane and 3 g. of p-toluenesulfonic acid were reacted andthe after-treatment was effected to give the end product as whitecrystals melting at 106°-107° C.

Analysis for C₁₅ H₂₉ NO₃ :

Calculated: C, 66.38%; H, 10.77%; N, 5.16%;

Found: C, 66.43%; H, 10.83%; N, 5.24%;

REFERENTIAL EXAMPLE 3 2,2,6,6-Tetramethylpiperidine-4-spiro-2'(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4"-(2'",2'",6'",6'"-tetramethylpiperidine) (Illustrated compound III-1)

163 g. of p-toluenesulfonate of triacetonamine, 17.6 g. ofpentaerythritol and 3 g. of p-toluenesulfonic acid were reacted andtreated in the same manner as shown in Referential Example 1 to give theend product as white crystals melting at 136.5°-137° C.

Analysis for C₂₃ H₄₂ N₂ O₄ :

Calculated: C, 67.28%; H, 10.31%; N, 6.82%.

Found: C, 66.98%; H, 10.28%; N, 6.76%.

REFERENTIAL EXAMPLE 48-Aza-2-hydroxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro-[4.5]decane(Illustrated compound IV-1)

To 12.4 g. of p-toluenesulfonate of triacetonamine were added 7 g. ofglycerine, 1 g. of p-toluenesulfonic acid and 25 ml. of toluene and themixture was reacted with heating at 110° C for 1 hour. After cooling,crystalline mass separated was recovered by filtration, 7 g. ofpotassium carbonate and 25 ml. of ice-water were added and extractionwith chloroform was done. The chloroform solution was concentrated afterdrying, the crystalline residue was recrystallized from ethanol to givethe end product as white crystals melting at 139°-140° C.

Analysis for C₁₂ H₂₃ NO₃ :

Calculated: C, 62.85%; J, 10.11%; N, 6.11%.

Found: C, 63.10%, H, 10.11%; N, 6.02%.

IR spectrum (Nujol mull): The absorption band of

ν_(C) _(=O) which was observed in the starting material

disappeared and the absorption bands of ν_(C-O) 1050 cm.sup.⁻¹

and ν_(OH) 3270 cm.sup.⁻¹ were seen.

REFERENTIAL EXAMPLE 52-Acetoxymethyl-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro-[4,5]decane(Illustrated compound IV-8)

In the wholly same manner as in Referential Example 4,p-toluenesulfonate of triacetonamine was reacted with glycerinemonoacetate to give the end product as colorless liquid of b.p. 128°C./2 mmHg.

Analysis for C₁₄ H₂₅ NO₄ :

Calculated: C, 61.96%; H. 9.29%; N, 5.16%.

Found: C, 62.20%; H, 9.38%; N, 5.32%.

IR spectrum (liquid film): ν_(C) _(=O) 1745 cm.sup.⁻¹, ν_(C-O)

1040 cm.sup.⁻¹,

NMR spectrum (CCl₄ soln.): 5.6-6.5 τ (5H, multiplet),

7.97 τ(3H, singlet), 8.4-8.6 τ(4H, broad doublet),

8.86 τ(12H, singlet).

REFERENTIAL EXAMPLE 6Cis-2,4,7-trioxabicyclo[3.3.0]octane-3-spiro-4'-(2',2',6',6'-tetramethylpiperidine)(Illustrated compound V-1)

To 21.4 g. of p-toluenesulfonate of triacetonamine were 10.2 g. ofmeso-erythritol, 2 g. of p-toluenesulfonic acid and 25 ml. of toluene,the reaction was effected with heating at 95°-100° C for 2.5 hours andthen under reflux for additional 6 hours. After cooling, crystallinemass separated was recovered by filtration, an 10% aqueous solution ofsodium hydroxide was added thereto and crystalline mass was separatedafter dissolution. The crystalline mass was recovered by filtration anddissolved in n-hexane. Then, the solution is dried and allowed to standunder cooling to separate crystals, which were recovered by filtrationto give the end product as white crystals melting at 87°-88° C.

Analysis for C₁₃ H₂₃ NO₃ :

Calculated: C, 64.70%; H, 9.61%; N, 5.80%.

Found: C, 64.58%; H, 9.55%; N, 5.73%.

IR spectrum (Nujol mull): The absorption band of ν_(C) _(=O)

seen in the starting material disappeared.

NMR spectrum (CDCl₃ soln.): 5.15-5.17 τ (2H,

multiplet, J=1 c/s), 5.94τ (2H, doublet, J=11 c/s),

6.57τ (2H, multiplet, J=11 c/s, J=1 c/s), 8.31 τ

(4H, doublet), 8.48τ (4H, doublet), 8.80 τ(12H,

singlet).

Mass spectrum: M⁺ m/e 241 (Calculated Molecular

Weight 241)

In accordance with the methods shown in Referential Examples 1 to 6, thefollowing compounds were synthesized.

The compounds of the formula (II):

9-aza-3-hydroxymethyl-3,8,8,9,10,10-hexamethyl-1,5-dioxa-spiro[5.5]undecane.bp 152°-154° C./3 mmHg.

9-Aza-9-(p-chlorobenzyl)-3-hydroxymethyl-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane. mp 143°-144° C.

9-aza-3-ethyl-3-hydroxymethyl-8,8,10,10-tetramethyl-9-(p-methylbenzyl)-1,5-dioxa-spiro[5.5]undecane.mp 145.5°-146° C.

9-aza-3-hydroxymethyl-3,8,8,10,10-pentamethyl-9-iodomethyl-1,5-dioxa-spiro[5.5]undecane.mp 216°-217° C. (decomp.)

9-Aza-9-benzyl-3-ethyl-3-hydroxymethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane.mp 110°-113° C.

The compounds of the formula (III):

1,2,2,6,6-pentamethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-(1'",2'",2'",6'",6'"-pentamethylpiperidine).mp 201.5°-203° C.

1-benzyl-2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-(1'"-benzyl-2'",2'",6'",6'"-tetramethylpiperidine).mp 211°-212° C.

The compounds of the formula (IV):

8-aza-2-hydroxymethyl-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro[4.5]decane.mp 77° C.

8-aza-8-benzyl-2-hydroxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.m. 93.5°-94.5° C.

2-acetoxymethyl-8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro[4.5]decane.bp 123°-125° C/0.5 mmHg

2-Acetoxymethyl-8-aza-8-benzyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 152°-154° C/0.002 mmHg

8-Aza-8-(2-hydroxyethyl)-2-hydroxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-sprio[4.5]decane.mp 94°-95° C.

8-acetyl-8-aza-2-hydroxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.mp 113°-114° C.

The compound of the formula (V).

Cis-2,4,7-trioxabicyclo[3.3.0]octane-3-spiro-4'-(1',2',2',6',6'-pentamethylpiperidine).mp 83°-84° C.

REFERENTIAL EXAMPLE 73-Acetoxymethyl-9-aza-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro-[5.5]undecane(Illustrated compound II-3)

To a solution of 20 g. of9-aza-3-hydroxymethyl-3,8,8,10,10,-pentamethyl-1,5-dioxa-spiro[5.5]undecaneand 26 g. of triethylamine in 100 ml. of ether was added 20 g. of acetylchloride under cooling to 5°-10° C.

After heating under reflux for 3 hours and cooling, an 10 % aqueoussolution of potassium carbonate was added and extraction with ether wasdone. The ether solution was dried and concentrated. The residue wasrecrystallized from ether to give the end product as white crystalsmelting at 95°-96° C.

Analysis for C₁₆ H₂₉ NO₄ :

Calculated: C, 64.18%; H, 9.76%; N, 4.68%.

Found: C, 64.17%; H, 9.60%; N, 4.62%.

IR spectrum (Nujol mull): ν_(c) _(=o) 1730 cm⁻ ¹

REFERENTIAL EXAMPLE 82-Acetoxymethyl-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro-[4.5]decane(Illustrated compound IV-8)

To 15 g. of8-aza-2-hydroxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decanewere added 27 g. of acetic anhydride and 25 ml. of chloroform anddissolved with heating. The reaction was conducted at room temperturefor 4 days to separate crystalline acetate of the end product. Afterrecovery by filtration and washing with ether, to 8.7 g. of the crystalwere added 7.2 g. of potassium carbonate, 10 g. of ice and 10 ml. ofwater and extraction with chloroform was done. The chloroform solutionwas washed with a saturated solution of sodium chloride in water, driedand the chloroform was distilled off. The liquid residue was subjectedto distillation under reduced pressure to give the end product ascolorless liquid of bp 112° C/1 mmHg, which was the same as obtained inReferential Example 5.

Analysis for C₁₄ H₂₆ NO₄ :

Calculated: C, 61.96%; H, 9.29%; N, 5.16%.

Found: C, 61.82%; H, 9.19%; N, 5.05%.

IR spectrum (liquid film): Wholly identified with that of the productobtained in Referential Example 5.

REFERENTIAL EXAMPLE 9Bis(8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]-2-decylmethyl)-terephthalate(Illustrated compound IV-76)

To 3 g. of8-aza-2-hydroxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decanewere added 1.3 g. of terephthaloyl chloride, 0.9 g. of potassiumcarbonate and 30 ml. of benzene and the reaction was effected by heatingunder reflux for 4 hours. After cooling, to the reaction liquid wasadded an 5% aqueous solution of potassium carbonate and extration withchloroform was done. The chloroform solution was dried and concentrated.The residue was cooled and the separated crystals were recovered byfiltration. The benzene solution of the crystal was poured into a silicagel column and from those fractions eluted from ethyl acetate was giventhe end product as white crystals melting at 134°-135° C.

Analysis for C₃₂ H₄₈ N₂ O₈ :

Calculated: C, 65.28%; H, 8.22%; N, 4.76%.

Found: C, 65.54%; H, 8.17%; N, 4.95%.

IR spectrum (Nujol mull): ν_(c) _(=o) 1730 cm⁻ ¹.

In accordance with the methods shown in the Referential Examples 7 to 9,the following compounds were synthesized.

The compounds of the formula (II):

3-acetoxymethyl-9-aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-spiro[5.5]undecane.mp 91°-92° C.

3-acryloyloxmethyl-9-aza-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane.mp 76°-79° C.

9-aza-3-benzoyloxymethyl-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane.mp 91°-92° C.

9-aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-3-stearoyloxymethyl-spiro[5.5]undecane.mp. 41°-42° C.

3-acetoxymethyl-9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane.mp 52°-53° C.

9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-3-stearoyloxymethyl-spiro[5.5]undecane.mp 43°-44° C.

9-aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-3-salicyloyloxymethyl-spiro[5.5]undecane.mp 69°-71° C.

9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-3-salicyloyloxymethyl-spiro[5.5]undecane.mp 117.5°-118.5° C.

Bis(9-aza-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]-3-undecylmethyl)adipate.mp 107°-108° C.

Bis(9-aza-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro-[5.5]-3-undecylmethyl)terephthalate.mp 127.5°-128.5° C.

3-acetoxymethyl-9-aza-9-benzyl-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane.mp 86°-88° C.

9-aza-3-ethyl-3-stearoyloxymethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane.mp 50°-52° C.

9-aza-3-benzoyloxymethyl-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane.mp 84°-86° C.

9-aza-3-benzoyloxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane.mp 84°-85° C.

9-aza-3-ethyl-3-salicyloyloxymethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane.mp 110°-111° C.

Bis(9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro-[5.5]-3-undecylmethyl)adipate.mp 87°-88.5° C.

Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]-3-undecylmethyl)adipate.mp 55.5°-57° C.

Bis(9-aza-3,8,8,9,10,10-hexamethyl-1,5-dioxa-spiro[5.5]-3-undecylmethyl)adipate.mp 130°-132° C.

Bis(9-aza-3-ethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro-[5.5]-3-undecylmethyl)terephthalate.mp 128°-129° C.

Bis(9-aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-spiro-[5.5]-3-undecylmethyl)terephthalate.mp 138°-140° C.

The compounds of the formula (IV):

2-acetoxymethyl-8-acetyl-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 123°-128° C/0.0007 mmHg.

8-Aza-2-butyryloxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]undecane. bp 150°-151° C/4 mmHg.

8-Aza-2-decanoyloxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]undecane.bp 190°-192° C/2 mmHg.

8-Aza-7,7,8,9,9-pentamethyl-1,4-dioxa-2-salicycloyloxymethyl-spiro[4.5]undecane.bp 188°-190° C/0.002 mmHg.

8-Aza-8-benzyl-7,7,9,9-tetramethyl-2-(m-toluoyloxymethyl)-1,4-dioxa-spiro[4.5]decane.bp 220°-226° C/0.001 mmHg.

8-Aza-2-(p-chlorobenzoyloxymethyl)-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 205°-207° C/2 mmHg.

2-(o-Anisoyloxymethyl)-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 215°-217° C/3 mmHg.

2-(o-Anisoyloxymethyl)-8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro[4.5]decane.bp 216°-223° C/1 mmHg.

Bis(8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]-2-decylmethyl)adipate.bp > 250° C/2 mmHg.

Bis(8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]-2-decylmethyl)sebacatep-toluenesulfonate. mp 145°-147° C.

Bis(8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]-2-decylmethyl)succinate.by > 250° C/2 mmHg.

8-Aza-7,7,9,9-tetramethyl-2-stearoyloxymethyl-1,4-dioxa-spiro[4.5]decane.mp 32°-34° C.

8-aza-7,7,8,9,9-pentamethyl-2-stearoyloxymethyl-1,4-dioxa-spiro[4.5]decane.mp 30°-34° C.

8-aza-7,7,9,9-tetramethyl-2-(m-toluoyloxymethyl)-1,4-dioxa-spiro[4.5]decane.bp 200°-203° C/3 mmHg.

8-Aza-7,7,9,9-tetramethyl-2-salicyloyloxymethyl)-1,4-dioxa-spiro[4.5]decane.mp 35°-37° C.

8-aza-2-benzoyloxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 192°-194° C/3 mmHg.

8-Aza-2-benzoyloxymethyl-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro[4.5]decane.bp 189°-191° C/0.2 mmHg.

Bis(8-aza-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro[4.5]-2-decylmethyl)terephthalate.mp 147°-148° C.

REFERENTIAL EXAMPLE 109-Aza-3-ethoxymethoxymethyl-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane(Illustrated compound II-51)

To a solution of 5 g. of9-aza-3-hydroxymethyl-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecaneand 5 g. of chloromethyl ethyl ether in 60 ml. of ether was added 10 ml.of triethylamine at 5°-10° C. and the reaction was effected at roomtemperature for 1 hour and with heating under reflux for additional 3hours. After cooling, 30 ml. of an 30% aqueous solution of potassiumcarbonate was added to the reaction liquid and extraction with ether wasdone. The ether solution was subjected to distillation under reducedpressure after drying to give the end product as colorless liquidboiling at 138°-140° C/3 mmHg.

Analysis for C₁₇ H₃₃ NO₄ : Calculated: C, 64.73%, H, 10.54%, N, 4.44%.Found: C, 64.35%; H, 10.43%; N, 4.41%.

REFERENTIAL EXAMPLE 112-Allyloxymethyl-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4,5]decane(Illustrated compound IV-59)

To a solution of 4.6 g. of8-aza-2-hydroxymethy7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decanedissolved in 20 ml. of dimethylformamide was added 1.1 g. of a 50%dispersion of sodium hydride in 0.2 g. of a 50% dispersion of sodiumhydride in 0.2 g. portions. After evolution of hydrogen ceases, thereaction was effected at room temperature for additional 1 hour. To thesolution was added 2.5 g. of allyl bromide under ice-cooling and thereaction was effected at room temperature for 1 hour and then at 45° Cfor additional 1 hour. Then, the reaction mixture was poured into 60 g.of ice and extraction with ether was done. The ether solution was driedand subjected to distillation under reduced pressure to give the endproduct as colorless liquid boiling at 114° C/2 mmHg.

Analysis for C₁₅ H₂₇ NO₃ : Calculated: C, 66.88%, H, 10.10%; N, 5.20%.Found: C, 66.94% H, 9.98%, N,5.08%.

IR spectrum (liquid film): ν_(C) _(=C) 1645 cm.sup.⁻¹.

In accordance with the method described in Referential Examples 10 and11, the following compounds were synthesized.

The compound of the formula (II),

9-aza-3-benzyloxymethyl-3,8,8,9,10,10-hexamethyl-1,5-dioxa-spiro[5.5]undecanne.bp 185°-187° C/0.8 mmHg.

The compound of the formula (IV),

8-aza-2-(2,3-epoxypropyloxymethyl)-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 132°-135° C/0.003 mmHg.

8-Aza-2-methoxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane. bp94°-95° C/2mmHg.

2-Allyloxymethyl-8-aza-7,7,8,9,9-pentamethyl-1,4-dioxaspiro[4.5]decane.bp 122°-124° C/1 mmHg.

8-Aza-2-benzyloxymethyl-7,7,9,9-tetramethyl-1,4-dioxaspiro[4.5]decane.bp 168°-170° C/1 mmHg.

REFERENTIAL EXAMPLE 122,2,6,6-Tetramethyl-1-octylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-(2'",2'",6'",6'"-tetramethylpiperidine)(Illustrated compound II-3(and2,2,6,6-tetramethyl-1-octylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1,,3'-dioxane(-2"-spiro-4'"-(2'", 2'", 6'",6'"-tetramethyl-1'"-octylpiperidine) (Illustrated compound III-4)

To 8.2 g. of2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-(2'",2'",6'", 6'"-tetramethylpiperidine) were added 8.5 g. of octyl bromide, 6.2g. of potassium carbonate and 0.5 g. of sodium acetate and heating waseffected at 185°-190° C. with stirring for 7 hours. After completion ofthe reaction, the potassium carbonate was filtered off, to the filtratewere added an aqueous solution of sodium hydroxide and benzene,separation of liquid was made by shaking, the benzene layer wasrecovered, dried and concentrated. The residue was flown into a silicagel column and fractions from elution with benzene gave crystallinemass, which was recrystallized from petroleum ether to give the endproduct, the N,N'-dioctyl derivative as white crystals melting at136°-137° C.

Analysis for C₃₉ H₇₄ N₂ O₄ Calculated: C, 73.76%, H, 11.75%, N, 4.41%.Found: C, 74.04%, H, 11.75%, N, 4.48%.

Then, fractions from elution with ether gave crystalline mass, which wasrecrystallized from petroleum ether to give the end product, theN-monooctyl derivative as white crystals melting at 104°-105.5° C.

Analysis for C₃₁ H₅₆ N₂ O₄ : Caculated: C, 71.21%, H, 11.18%; N, 5.36%.Found: C, 71.36%, H, 11.19%; N, 5.45%.

REFERENTIAL EXAMPLE 132-Acetoxymethyl-8-aza-8-ethoxycarbonylmethyl-7,7,9,9-tetramethyl1,4-dioxa-spiro[4,5]decane(Illustrated compound IV-17)

To 4 g. of2-acetoxymethyl-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decanewere added 0.6 g. of sodium hydroxide, 0.3 of sodium iodide and 20 ml.of benzene and to the resulting suspension was added 3.7 g. of ethylmonobromoacetate at 10° C. The reaction was effected at room temperatureand then at 50°-60° C. for additional 1 hour. After cooling, to thereaction liquid was added an 5% aqueous solution of potassium carbonateand extraction with benzene was done. The benzene solution was washedwith a saturated solution of sodium chloride in water, dried andconcentrated. The residue was chromatographed with a silica gel column,fractions from elution with a solvent of benzene:n-hexane:ethyl acetate=4:2:1 gave crystalline mass, which was then recrystallized frompetroleum ether to give the end product as white crystals at 82°-83° C.

Analysis for C₁₈ H₃₁ NO₆ : Calculated: C, 60.48%; H, 8.74%, N, 3.93%.Found: C, 60.20%; H, 8.65%, N, 3.66%.

IR sprectrum (Nujol mull): ν_(C) _(=O) 1745, 2735, cm.sup.⁻¹ .

In accordance with the method described in Referential Examples 12 and13, the following compounds were synthesized,

The compounds of the formula (II):

9-aza-3-(2-epoxypropyloxymethyl)-3,8,8,9,10,10-hexamethyl-1,5-dioxa-spiro[5.5]undecane.bp 159°-160° C/1 mmHg.

3-Acetoxymethyl-9-aza-9-(2,3-epoxypropyl)-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane.mp 106°-107° C.

3-acetoxymethyl-9-aza-9-benzyloxycarbonyl-3,8,8,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecane. mp 96.5°-97.5° C.

3-acetoxymethyl-9-aza-3-ethyl-9-methoxycarbonylmethyl-8,8,10,10-tetramethyl-1,5-dioxa-spiro[5.5]undecane mp 65°-67.5° C.

The compounds of the formula (III).

1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-[1'"-(2-acetoxyethyl)-2'",2'",6'",6'"-tetramethylpiperidine].mp 194°-195° C.

1-(2-acetoxyethyl)-2,2,6,6-tramethypiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4"-[1'"-(2-acetoxyethyl)-2'",2'",6'",6'"-tetramethylpiperidine].mp 172°-183° C.

1-(2-acryloyloxyethyl)-2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3",-dioxane)-2"-spiro-4''-[1'"-(2-acryloyloxyethyl)-2'",3'",6'", 6'"-tetramethylpiperidine]. mp 162°-163° C.

1-82-benzoyloxyethyl)-2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-[1'"-(2-benxoyloxyethyl)-'",2'",6'",6'"-tetramethylpiperidine].mp 243°-245° C.

1-82,3-epoxypropyl)-2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro5"-(1",3"-dioxane)-2"-spiro-4'"-[1'"-(2,3-epoxypropyl)-2'",2'",6'",6'"tetramethylpiperidine].mp 157°-159° C.

2,2,6,6-Tetramethyl-1-(2-stearoyloxyethyl)piperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-[2'",2'",6'",6'"-tetramethyl-1'"-(2-stearoyloxyethyl)piperidine].mp 70°-72° C.

2,2,6,6-tetramethyl-1-methoxycarbonylmethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4'"-(2'",2'",6'",6'"-tetramethyl-1'"-methoxycarbonylmethylpiperidine).mp 165°-167° C.

1-allyl-2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"spiro4'"-(1'"-allyl-2'",2'",6'",6'"-tetramethylpiperidine). mp 158°-159° C.

The compounds of the formula (IV):

2-acetoxymethyl-8-allyl-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 150°-153° C/1 mmHg.

2-Acetoxymethyl-8-aza-8-benzyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 152°-154° C/0.002 mmHg.

2-Acetoxymethyl-8-aza-8-(2,3-epoxypropyl)-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 162°-165° C/0.002 mmHg.

2-Acetoxymethyl-8-aza-8-(2-hydroxyethyl)-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 154°-153° C.0.0008 mmHg.

2-Acetoxymethyl-8-(2-acetoxymethyl)-8-aza-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.bp 159°-162° C/0.0004 mmHg.

2-Acetoxymethyl-8-aza-8-cyanomethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.mp 59°-60° C.

8-aza-8-(2-benzoyloxyethyl)-2-benzoyloxymethyl-7,7,9,9-tetramethyl-1,4-dioxa-spiro[4.5]decane.mp 110°-111° C.

8-aza-2-(p-chlorobenzoyloxymethyl)-7,7,9,9-tetramethyl-1,4-dioxa-8-(2-propynyl)-spiro[4.5]decane.mp 102°-103° C.

The compound of the formula (V):

Cis-2,4,7-trioxabicyclo[3.3.0]octane-3-spiro-4'-(1',2',2',6',6'-pentamethylpiperidine). mp83°-84° C.

REFERENTIAL EXAMPLE 149Aza-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-3-phenylcarbamoyloxymethyl-spiro[5.5]undecane(Illustrated compound II-44)

To 3 g. of9-aza-3-ethyl-3-hydroxymethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-spiro[5.5]undecanewere added 2 ml. of triethylamine and 30 ml. of benzene and to thesolution was added with stirring a solution of 1.3 g. of phenylisocyanate dissolved in 20 ml. of benzene. The reaction was effectedwith heating at 70°-75° C. for 4.5 hours. The reaction liquid wasconcentrated and the residual liquid was flown into a silica gel column.Elution with a mixed solvent of benzene-ether (1:1) gave crystallinemass, which was then recrystallized from petroleum ether to give the endproduct as white crystals melting at 94° C.

Analysis for C₂₃ H₃₆ N₂ O₄ : Calculated: C, 68.28%; H, 8.97%; N, 6.93%.Found: C, 68.39%; H, 8.88%; N, 6.85%.

In accordance with the method as shown in Referential Example 14, thefollowing compounds were synthesized.

The compounds of the formula (IV):

8-aza-2-ethylcarbamoylmethyl-7,7,8,9,9-pentamethyl-1,4-dioxa-spiro[4.5]decane.bp 156° -160° C/0.003 mmHg.

1,4-dioxa-2-phenylcarbamoyloxymethyl-spiro[4.5]decane. bp 170°-172°C/0.0004 mmHg.

What we claim is:
 1. A compound having the formula ##STR18## wherein R₁represents hydrogen atom, methyl, er acetyl.
 2. A compound as claimed inclaim 1 wherein R₁ is hydrogen atom or methyl group.